US3644526A - Oxidation of cyclohexane - Google Patents

Oxidation of cyclohexane Download PDF

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Publication number
US3644526A
US3644526A US802352A US3644526DA US3644526A US 3644526 A US3644526 A US 3644526A US 802352 A US802352 A US 802352A US 3644526D A US3644526D A US 3644526DA US 3644526 A US3644526 A US 3644526A
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catalyst
cyclohexane
reaction
borate
cobalt
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US802352A
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English (en)
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Kazumi Takagi
Takaharu Ishida
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C07C29/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only in the presence of mineral boron compounds with, when necessary, hydrolysis of the intermediate formed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • Cyclohexane is oxidized in a liquid phase in the presence of such a heterogeneous catalyst as a manganese or cobalt borate, particularly a cobalt borate having a Co/B2 molar ratio of 0.5 to 4, whereby the excessive oxidation of cyclohexane and the formation of a borate ester of cyclohexanol can be inhibited and cyclohexanone and cyclohexanol can be produced advantageously.
  • a heterogeneous catalyst as a manganese or cobalt borate, particularly a cobalt borate having a Co/B2 molar ratio of 0.5 to 4
  • This invention relates to the oxidation of cyclohexane. More particularly, the invention pertains to a process in which cyclohexane is oxidized in a liquid phase in the presence of a heterogeneous catalyst to produce cyclohexanol and cyclohexanone.
  • a process for oxidizing cyclohexane in a liquid phase with oxygen or an oxygen-containing gas by using as a catalyst such a soluble cobalt compound as cobalt naphthenate or cobalt acetate has already been well known.
  • the oxidation is effected in a homogeneous phase and the catalyst is maintained in a homogeneous system throughout the reaction.
  • the reaction product obtained according to the above-mentioned process is mostly a 1:1 mixture of cyclohexanol and cyclohexanone.
  • boric acid is required to be used in an amount more than the stoichiometric amount necessary for the formation of a borate ester of cyclohexanol, and that the steps are complex in that the cyclohexanol should be recovered by hydrolyzing the thus formed borate ester.
  • An object of the present invention is to provide a novel process for the liquid phase oxidation of cyclohexane in which is used a heterogeneous catalyst.
  • Another object is to provide a process for the oxidation of cyclohexane in which the excessive oxidation of cyclohexane is inhibited and no complex step is required.
  • the present inventors made various studies to find that when a transition metal borate such as cobalt borate or manganese borate is made present in a suspended state in the reaction system, said borate not only acts as an effective catalyst but also displays an elfect of preventing excessive oxidation, with the result that the amounts of the aforesaid fatty acids formed can be made smaller than in the case of conventional processes and, at the same time, it becomes possible to overcome the drawbacks encountered in the case where boric acid or a mixture thereof with an organic acid salt of cobalt is used. Based on the above iinding, the inventors have established the present invention.
  • a process for oxidizing cyclohexane in which cyclohexane is oxidized in a liquid phase With molecular oxygen or inert gas-diluted oxygen in the presence of, as a catalyst, a transition metal borate or a cobalt borate having a C ⁇ o/B2 molar ratio within the range from 0.5 to 4.
  • the oxidation takes place in a heterogeneous phase and the catalyst, which includes such borates as detailed below, is scarcely soluble in the reaction liquid or in cyclohexane and can be simply separated by filtration.
  • the transition metal borate referred to herein signiiies a borate of cobalt, manganese or the like transition metal or a mixture of 2 or more of such borates.
  • This catalyst is diicultly soluble in cyclohexane and in the oxidation reaction liquid, and dissolves to a me-tal concentration of only about less than l ppm., so that it is an entirely heterogeneous catalyst. Since the catalyst is high in specific gravity, it can be readily separated according to precipitation method and can be used repeatedly. Further, this catalyst does not form an ester with cyclohexanol, unlike the case of conventional boric acid catalysts. However, if water is present in the reaction system, the catalyst dissolves in the aqueous phase to bring about degradation in catalyst activity and diculty of recovery. It is therefore desirable that the catalyst be used under conditions where no water is present as far as possible.
  • transition metal borates which are the catalysts employed in the present process
  • the attached drawing shows the equilibrium State in composition of COO-B203 system catalysts.
  • the compositions of the present catalysts are represented by the regions where the Co/B2 molar ratio is within the range of 0.5 to 4.
  • those having a Co/BZ molar ratio of l to 3, especially 2 to 3, are particularly preferable.
  • a borate having a Co/Bz molar ratio of less than 0.5 water of crystallization tends to be isolated during the reaction to liberate boric acid, or free boric acid tends to be incorporated at the time of preparation, with the result that a borate ester of cyclohexanol produced is undesirably formed.
  • the said Co/B2 molar ratio should not be made more than 4. Free boric acid formed during the preparation of catalyst can be removed by washing with water or alcohol.
  • the catalyst may be synthesized according to the aforesaid melting or sintering process, whereby it can be directly used in the reaction without adoption of any other treatment step than mere pulver-ization. If necessary, the catalyst according to the present invention may be supported on a carrier.
  • the oxidation reaction of cyclohexane in the presence of the present catalyst can be effected at a reaction temperature within such a Wide range of about 100 to 300 C., preferably 100 to 200 C.
  • the reaction pressure to be adopted may be within such a range that the starting cyclohexane can maintain a liquid phase at the abovementioned reaction temperature, and is within the range of normal pressure to 100 kg./cm.2 (gauge), preferably normal pressure to kg./cm.2 (gauge). Under such conventional conditions in this technical field, a sufiicient reaction rate can be attained and cyclohexanone and cyclohexanol can be obtained in high yields.
  • the oxidation reaction is carried out under the aforesaid reaction temperature and pressure conditions while injecting an oxidizing gas in a proportion of 1-100 l./hr. per 100 g. of the starting cyclohexane.
  • the oxidizing gas referred to herein includes oxygen and oxygen or air which has been properly diluted with such an inert gas as nitrogen or the like.
  • the amount of the catalyst to be added is 0.0l-20.0 parts (by Weight), preferably 0.1-5.0 parts, per 100 parts of the fed cyclohexane (the staying cyclohexane in the case where the reaction is effected in a continuous manner).
  • the grain size of the catalyst may be 300 mesh or less, in general. If the catalyst is ground more finely or is supported on a carrier such as alumina or the like, the amount of the catalyst can further be reduced. Since the catalyst is insoluble in the reaction liquid, the excessive use thereof is not desirable from the standpoint of handling.
  • 'I'he catalyst of the present invention can display its effects also in the case of continuous oxidation.
  • cyclohexane can be oxidized to cyclohexanol and cycloliexanone with high selectivity. Moreover, the separation of these products from the catalyst can be easily effected and the catalyst is readily reusable.
  • EXAMPLE 2 A mixture comprising 465 g. of cyclohexane and 10 g. of cobalt carbonate, which is a heterogeneous system inorganic acid salt other than borate, was fed to the same autoclave as in Example 1. Into the autoclave was injected a mixed gas composed of 5 parts by Volume of O2 and 95 parts by volume of N2 in a proportion of 75 l./hr. through the gas inlet under such conditions as a temperature of C. and a pressure of 9.5 kg./cm.2 abs., but no reaction took place even after 2 hours.
  • a mixed gas composed of 5 parts by Volume of O2 and 95 parts by volume of N2 in a proportion of 75 l./hr. through the gas inlet under such conditions as a temperature of C. and a pressure of 9.5 kg./cm.2 abs., but no reaction took place even after 2 hours.
  • EXAMPLE 3 A mixture comprising 465 g. of cyclohexane and 5 g. of cobalt borate was fed to the same autoclave as in Example 1. Into the autoclave was injected a mixed gas composed of 10 parts by volume of O2 and 90 parts by volume of N2 in a proportion of 75 L/hr. through the gas inlet under such conditions as a temperature of C. and a pressure of 9.5 14g/cm.2 abs. After 1.5 hours reaction, the reaction liquid was quenched and the catalyst was separated by filtration. Subsequently, the filtrate was directly subjected to reduced pressure distillation and the distillate was analyzed to obtain 17.83 g. of cyclohexanone and 16.38 g. of cyclohexanol with a conversion of 6.87%.
  • Comparative Example 1 22.3 g. of 2CoCO33Co(OH)2 was sufficiently homogeneously mixed in a mortar with 98.0 g. of H3BO3. The mixture was heated in an electric furnace in open air at 450 C. for 3 hours and then at 900 C. for 2 hours. The melt was cooled with air to obtain a bluish white glasslike substance. This substance was pulverized to 100- 200 mesh and was used as a catalyst in the subsequent reaction. The said substance contained a large amount of free boric acid anhydride.
  • a mixture comprising 5.56 moles of cyclohexane and g. of the catalyst synthesized in the above-mentioned manner was fed to the same autoclave as in Example 1 and was oxidized with air for 1.5 hours under such conditions as 160 C. and 9.5 kg./cm.2 abs. The reaction progressed quickly but the reaction rate gradually lowered. The reaction liquid taken out was brown, and a black brown solid had adhered to the reactor wall. The reaction liquid was charged with a small amount of water and was then boiled to obtain 5.07 moles of cyclohexane, 0.290 mole of cyclohexanol, 0.092 mole of cyclohexanone and 8.02 g. of brown high boilings.
  • Comparative Example 2 88.0 g. of 2CoCO33Co(OH)2 was suiiiciently homogeneously mixed in a mortar with 21.1 g. of H3BO3. The mixture was heated in an electric furnace in open ai-r at 450 C. for 3 hours and then at 1100 C. for 2 hours. The melt was cooled with air to room temperature to obtain a black substance. This substance contained cobalt oxide. The substance was pulverized and was used as a catalyst in the subsequent reaction. It was confirmed that no free boric acid had migrated in said substance.
  • a mixture comprising 5.56 moles of cyclohexane and 5 g. of the above-mentioned catalyst was fed to the same reactor as in Example 1 and was oxidized with air for 1.5 hours under such conditions as 140 C. and 9.5 kg./ cm.2 abs.
  • the reaction progressed quickly and no such lowering in reaction rate as in Comparative Example 1 was observed.
  • the reactor was cooled with air after the reaction and the reaction liquid was taken out of the reactor, it was Irecognized that a black brown rubbery substance was present in the reactor in addition to the catalyst. From the reaction liquid were recovered 5.15 moles of cyclohexane, 0.19 mole of cyclohexanol, 0.15 mole of cyclohexanone and 1.31 g. of rubbery high boilings.
  • EXAMPLE 5 79.5 g. of 2CoCO3-3Co(OH)2 was suiciently homogeneously mixed in a mortar with 31.0 g. of H3BO3. The mixture was treated in the same manner as in Comparative Example 2 to obtain a reddish purple substance. This substance was pnlverized and was used as a catalyst in the subsequent reaction. After confirming that the catalyst contained no free boric acid, the same reaction as in Comparative Example 2 was effected. After lthe reaction, the
  • EXAMPLE 6 125.0 g. of Co(CH3COC)2-4H2O was sutliciently homogeneously mixed in a mortar with 62 g. of H3BO3. The mixture was heated in an electric furnace in open air at 450 C. for 3 hours and then at 850 C. for 2 hours. The melt was cooled with air to room temperature to obtain a reddish purple substance in which had been formed COO-B203. This substance was puverized and was then used as a catalyst in the subsequent reaction. It was confirmed that a slight amount of free boric acid was present in said substance.
  • a mixture comprising 5 .56 moles of cyclohexane and 5 g. of said catalyst was fed to the same reactor as in Example 1 and was oxidized with air for 1.5 hours under such conditions as 160 C. and 9.5 kg./cm.2 abs. After the reaction, the reaction liquid was taken out and the catalyst was separated by filtration. From the filtrate were recovered 5.16 moles of cyclohexane, 0.24 mole of cyclohexano1 and 0.12 mole of cyclohexanone. Such high boilings as in Comparative Examples 1 and 2 were scarcely formed.
  • a process for oxidizing cyclohexane which comprises subjecting cyclohexane to liquid phase oxidation with m0- lecular oxygen or inert gas-diluted oxygen at a temperature of to 300 C. in the presence of cobalt borate or manganese borate.
  • a process for oxidizing cyclohexane which comprises subjecting cyclohexane to liquid phase oxidation with molecular oxygen or inert gas'diluted oxygen at a temperature of 100 to 300 C. in the presence of a cobalt borate having a Co/B2 molar ratio of 0.5 to 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US802352A 1968-03-06 1969-02-26 Oxidation of cyclohexane Expired - Lifetime US3644526A (en)

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Application Number Priority Date Filing Date Title
JP1482968 1968-03-06
JP7760468 1968-10-23

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US (1) US3644526A (nl)
BE (1) BE729400A (nl)
CH (1) CH515867A (nl)
DE (1) DE1911288A1 (nl)
FR (1) FR2003318A1 (nl)
GB (1) GB1208386A (nl)
NL (1) NL6903390A (nl)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4863888A (en) * 1988-04-29 1989-09-05 Amoco Corporation Catalyst containing cobalt boron and oxygen and optionally aluminum of preparation and process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4863888A (en) * 1988-04-29 1989-09-05 Amoco Corporation Catalyst containing cobalt boron and oxygen and optionally aluminum of preparation and process

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Publication number Publication date
NL6903390A (nl) 1969-09-09
CH515867A (de) 1971-11-30
BE729400A (nl) 1969-08-18
DE1911288A1 (de) 1969-10-02
FR2003318A1 (nl) 1969-11-07
GB1208386A (en) 1970-10-14

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